Aqueous plastic material dispersions method for producing the same and use thereof

ABSTRACT

The present invention relates to aqueous plastic material dispersions based on vinyl ester copolymers, having a solids content of up to 80% by weight and a minimum film formation temperature below 20° C., which is substantially stabilized by ionic components, the vinyl ester copolymers containing at least one homo- or copolymer A and at least one homo- or copolymer B, methods for producing the same and the use thereof.

This application is a 371 of PCT/EP02/02817 filed Mar. 14, 2002.

The present invention relates to aqueous plastic material dispersionsbased on vinyl ester copolymers which are substantially stabilized byionic components, methods for producing the same and the use thereof.

Plastic material dispersions are used as binders for the preparation ofboth pigmented and unpigmented, aqueous formulations which are used, forexample, as coating materials. The pigmented coating materials includein particular glazes, emulsion finishes, emulsion paints, syntheticresin-bound renders, sealing compounds and filling compounds, which arewidely used both in the protection of buildings and in the decorativesector. The unpigmented coating materials include, for example, clearfinishes. Moreover, plastic material dispersions are the main componentof water-based food coatings which are intended to protect the substratefrom drying out and harmful environmental influences.

Said coating materials can be divided into two classes depending on theproportion of plastic material dispersions in the total coatingcomposition. Glazes, emulsion finishes and gloss paints can be assignedto the class consisting of the subcritically formulated coatingcompositions, which have a pigment volume concentration (PVC) below theso-called critical PVC. On the other hand there are supercritical,pigment-containing coating materials, such as, for example, interiorpaints or synthetic resin-bound renders having a high filler content.These have a pigment volume concentration above the critical pigmentvolume concentration and are formulated with a substantially lowercontent of polymeric binder. These two classes of coating compositionmust meet a multiplicity of practical requirements. Common to bothclasses is that, in addition to good processibility of the aqueousformulations even at low processing temperatures, blocking resistance ofthe dried coating and resistance of the coatings to abrasion are amongthe most important performance characteristics.

In the case of binder-rich coating compositions (low PVC) whose surfacesare characterized by a high content of polymeric binder, glossproperties of the dried coating are also of primary importance apartfrom the blocking resistance and abrasion resistance.

Conventional coating materials based on aqueous plastic materialdispersions meet these requirements with regard to binder-rich coatingcompositions if, as a rule, a polymer having a relatively high glasstransition temperature (relatively hard polymer) is used as a binder andsmall amounts of film formation auxiliaries, such as, for example,organic solvents (e.g. hydrocarbons) and/or plasticizers (e.g. phthalicesters or glycol ethers) are added in order to reduce the minimum filmformation temperature (MFT), i.e. the temperature above which thepolymer in the formulation is converted into a film, and to ensure filmformation of the polymer even at relatively low processing temperatures.Solvents and volatile plasticizers are liberated on drying theformulation, with the result that the mechanical strength of the coatingis increased or the surface hardness and hence the blocking resistanceof the paint formulation increase. However, owing to their harmfuleffect on man and the environment, the abrasion of volatile organiccomponent is not desired, particularly in applications indoors.

There therefore was and is a considerable need for aqueous plasticmaterial dispersions which make it possible to formulate plasticizer-and solvent-free coating systems having high binder contents (low PVC)and a low film formation temperature, which meet the requirements withregard to blocking resistance, gloss properties and abrasion properties.

In contrast to the required performance characteristics of binder-richcoating systems, in the case of so-called high-filler coating systemswhich are formulated with a low binder content (high PVC), sufficientblocking resistance is usually present at the coating surface owing tothe high proportion of fillers and pigments. Instead, in particular theresistance of the dried coatings to abrasion (abrasion resistance) is ofprimary importance as a performance characteristic for these coatingsystems.

As in the case of conventional, binder-rich coating materials, therequired properties are achieved in the case of conventional high-fillercoating materials by using a polymer having a relatively high glasstransition temperature (relatively hard polymer) as a binder togetherwith small amounts of a film formation auxiliary, which however is onceagain released into the environment on drying of the formulation.

In combination with film formation auxiliaries, polymers having arelatively high glass transition temperature thus serve as universalbinders for the preparation of conventional coating materials havinghigh and low PVCs, which can be processed at low temperatures.

In view of this universal applicability of conventional binder systems,there was and is, over and above the need for aqueous plastic materialdispersions which make it possible to formulate plasticizer- andformulation-free coating systems having low PVCs and a low filmformation temperature, which meet the requirements with regard toblocking resistance, gloss properties and abrasion properties, also aconsiderable need for universally applicable, aqueous plastic materialdispersions which make it possible to formulate plasticizer- andsolvent-free coating systems both having high and having low PVCs and alow film formation temperature, which meet the requirements with regardto blocking resistance, gloss properties and abrasion resistance.

DE-A-198 11 314 discloses multistage acrylic ester dispersions whichcontain itaconic acid as an acidic comonomer and are preferably preparedusing anionic emulsifiers or using mixtures of anionic and nonionicemulsifiers as stabilizers. The binders described have advantageous wetabrasion resistances and blocking resistances, but only inplasticizer-containing paint formulations having a low PVC of 46.9%.

EP-A-0 347 760 leaves a special sulfosuccinamide salt as a subsequentadditive and/or a stabilizer during the polymerization of acrylic esterand styrene/acrylic ester dispersions is recommended. With the bindersthus obtained, plasticizer-containing gloss finishes having highblocking resistance can be produced. On the other hand, all other ionicemulsifiers investigated have no effect.

EP-A-0 609 756 discloses multistage acrylic ester, styrene/acrylic esterand vinyl/acrylic ester dispersions, it being necessary for one of thepolymer phases to have a glass transition temperature in the range from−55 to −5° C. and a further polymer phase to have a glass transitiontemperature in the range from 0 to 50° C. For the preparation of thesedispersions, at least one anionic emulsifier and optionally at least onenonionic emulsifier are preferably used. In the examples, stabilizersystems consisting of nonionic and ionic emulsifiers in the ratio ofabout 1:1 are disclosed. They show that the solvent-free semi-gloss,satin and silk paint examples formulated using the binders according tothe invention have blocking resistances which are comparable with thesolvent-containing systems, which is achieved by the presence of twopolymer phases having the special glass transition temperature ranges.

EP-A-1 018 835 describes solvent-free coating compositions havingimproved blocking resistance, which contain, as a binder, a mixture ofan acrylic ester copolymer dispersion and a vinyl ester copolymerdispersion. Characteristic of the acrylic ester component used in lessthan the required amount in the dispersion mixture is not only thenecessary copolymerization of sterically hindered silanes but also theuse of at least one anionic emulsifier during the preparation of thisdispersion component for achieving the desired high blocking resistancesof the coating compositions prepared using these binders. According tothe teaching of this publication, the exclusive use of nonionicsurfactants in the preparation of the acrylic ester component leads toinsufficient blocking resistances. In contrast, the nature of theemulsifier which is used in the preparation of the vinyl ester componentemployed in excess has no effect on the blocking resistance of theresulting coatings.

Vinyl ester dispersions having heterogeneous morphology are described ina number of patent applications.

Thus, DE-A-198 53 461 discloses protective colloid-stabilized copolymerlatex particles having heterogeneous morphology, which are composed of ahard and a soft polymer phase, the preferred glass transitiontemperatures of the individual phases being from −40 to +20° C. and from+20 to +35° C., respectively. The emulsion polymerization for thepreparation of these dispersions, from which dispersion powders areprepared after they have been dried, stipulates the use of protectivecolloids. Surface-active substances, such as, for example, emulsifiers,can optionally be used. Also disclosed is the use of the copolymer latexparticles as a binder in emulsion paints and renders.

DE-A-197 39 936 discloses plasticizer-free, heterogeneous vinylacetate/ethene dispersions which are substantially stabilized withpolyvinyl alcohol as protective colloid and are prepared by seedpolymerization of a copolymer A having a glass transition temperatureof >20°C. in the presence of a seed base comprising a copolymer B havinga glass transition temperature of <20° C.

The dispersions described above in DE-A-198 53 461 and DE-A-197 39 936are substantially stabilized by protective colloids. Owing to theassociated high content of water-soluble, readily swellable, polymericstabilizers, coating compositions which contain these dispersions of thebinder are expected to have a high water absorption of the coating whichleads to a low abrasion resistance under abrasive load in the swollenstate.

EP-A-0 444 827 describes vinyl ester/ethene/acrylic ester dispersionshaving a core-shell morphology, the composition of the polymer phases ofcore and shell being chosen so that the copolymer has only a glasstransition temperature in the range from −30 to 0° C. By means of thevinylsilane copolymerization also prescribed, dispersions which aresuitable as advantageous binders for crack-bridging coating materialsare obtained. The low glass transition temperature of the core-shellcopolymer does however rule out the use of these soft copolymerdispersions as binders for the formulation of blocking-resistant,binder-rich coating compositions.

It was therefore an object of the present invention to overcome thedisadvantages of the known, heterogeneous vinyl ester dispersions, inparticular the insufficient blocking resistance of the binder-richcoating compositions formulated using these dispersions, and to providenovel vinyl ester dispersions which make it possible to provideplasticizer- and solvent-free coating compositions having a high bindercontent (e.g. coating compositions having a PVC lower than the criticalPVC), which form crack-free coating films at low temperatures and aredistinguished by improved blocking resistance.

Surprisingly, it was found that, contrary to the information from theprior art, the composition of the stabilizing system of vinyl esterdispersions has a substantial effect on the blocking resistance ofcoatings which are based on these binders. Accordingly, the object ofthe present invention is achieved by providing heterogeneous plasticmaterial dispersions based on vinyl ester copolymers, which aresubstantially stabilized by ionic components.

The present invention therefore relates to an aqueous plastic materialdispersion based on a vinyl ester copolymer P, having a solids contentof up to 80% by weight and a minimum film formation temperature below20° C., which is substantially stabilized by ionic components, the vinylester copolymer P comprising at least one homo- or copolymer A and atleast one homo- or copolymer B, preferably at least one copolymer A andat least one copolymer B, particularly preferably a copolymer A and acopolymer B, and

-   -   the homo- or copolymer A having a glass transition temperature        in the range from 0 to 20° C. and the homo- or copolymer B        having a glass transition temperature in the range from 20 to        50° C., provided that the glass transition temperatures of the        two homo- or copolymers A and B differ by at least 10 K,    -   the sum of the amounts of the homo- or copolymers A and B in the        vinyl ester copolymer P being at least 50% by weight, based on        the copolymer P,    -   the weight ratio of homo- or copolymer A to homo- or copolymer B        being in the range from 95/5 to 5/95 and    -   the homo- or copolymers A and B, independently of one another,        containing in the form of copolymerized units        -   (a) from 50 to 100% by weight of at least one vinyl ester of            carboxylic acids having 1 to 18 C atoms (M1) and        -   (b) from 0 to 25% by weight of at least one            monoethylenically unsaturated, optionally            halogen-substituted hydrocarbon having 2 to 4 C atoms (M2),            also referred to below as monoolefin having 2 to 4 C atoms,            based on the total mass of the monomers used for the            preparation of the respective homo- or copolymer A and B,            which is characterized in that it comprises, based on the            total mass of the monomers used for the preparation of the            vinyl ester copolymer P,    -   from 0 to 10% by weight of at least one ethylenically        unsaturated, ionic monomer (M3) and    -   from 0 to 5% by weight of ionic emulsifiers (S1),    -   the total mass of ethylenically unsaturated, ionic monomers (M3)        and ionic emulsifiers (S1) being at least 2% by weight.

The term solids content is understood in the present application asmeaning the total mass of copolymer, based on the total mass of thedispersion. The solids content of the plastic material dispersionsaccording to the invention is preferably in the range from 20 to 80% byweight, particularly preferably in the range from 40 to 70% by weightand in particular in the range from 45 to 60% by weight.

The sum of the amounts of homo- or copolymers A and B in the vinyl estercopolymer P is preferably from 75 to 100% by weight, particularlypreferably from 80 to 100% by weight and in particular from 85 to 100%by weight, based on the total mass of the copolymer P.

The weight ratio of homo- or copolymer A to homo- or copolymer B ispreferably in the range from 90/10 to 10/90, particularly preferably inthe range from 80/20 to 20/80 and in particular in the range from 70/30to 30/70.

The size of the homo- or copolymer particles of the dispersionsaccording to the invention may vary within wide ranges. However, themean particle diameter preferably should not exceed 1 000 nm andparticularly preferably should not exceed 600 nm. With regard to optimumcoating properties, the average particle diameter should in particularbe less than 350 nm. In the case of binder dispersions having highsolids contents of more than 60% by weight, based on the total weight ofthe binder dispersions, it is however particularly preferred, forreasons relating to the viscosity, if the mean particle diameter isgreater than 140 nm.

The plastic material dispersions according to the invention preferablyhave a pH which is in the range from 2 to 9 and particularly preferablyin the range from 3 to 7.

The minimum film formation temperature of the heterogeneous vinyl esterdispersions according to the invention are 20° C. Preferably, theminimum film formation is below 10° C., particularly preferably below 5°C. and in particular below 0° C.

In a preferred embodiment of the present invention, the vinyl estercopolymer particles of the dispersions according to the invention are,in the widest sense, multistage polymers having at least one softpolymer phase (i.e. low Tg) and at least one hard polymer phase (i.e.high Tg), which can be prepared, for example, by multistage emulsionpolymerization, the polymerization of the subsequent stage(s) beingeffected in the presence of the previously formed polymerizationstage(s). Particularly preferably, the multistage polymerizationprocesses by means of which the plastic material dispersions accordingto the invention can be prepared are two-stage processes.

In addition, the vinyl ester copolymers P of the plastic materialdispersions according to the invention can, however, also be obtained bymixing at least two homo- or copolymers A and B prepared beforehandseparately in dispersion form.

In the present application, the glass transition temperatures of thehomo- or copolymers A and B are calculated according to a Fox equation(T. G. Fox, Bull. Am. Phys. Soc. (Ser. II) 1, 123 [1956] and Ullmann'sEnzyklopädie der technischen Chemie [Ullmann's Encyclopedia ofIndustrial Chemistry], Weinheim (1980), Volume 19, pages 17–18),according to which a good approximation for the glass transitiontemperature Tg of copolymers having high molar masses is the equation

$\frac{1}{T_{g}} = {\frac{X^{1}}{T_{g}^{1}} + \frac{X^{2}}{T_{g}^{2}} + {\ldots\mspace{11mu}\frac{X^{n}}{T_{g}^{n}}}}$in which X¹, X², . . . , X^(n) are the mass fractions 1, 2, . . . , nand T_(g) ¹, T_(g) ², . . . , T_(g) ^(n) are the glass transitiontemperatures, in degrees Kelvin, of the polymer composed in each caseonly of one of the monomers 1, 2, . . . , n. The latter are known, forexample, from Ullmann's Enzyclopädia of Industrial Chemistry, V C HWeinheim, Vol. A 21 (1992), page 169, or from Brandrup, E. H. Immergut,Polymer Handbook 3^(rd) ed, J. Wiley, New York 1989, such as, forexample, the glass transition temperature 148 K of the ethenehomopolymer (cf. Brandrup, E. H. Immergut, Polymer Handbook 3^(rd) ed,J. Wiley, New York 1989, page VI/214) and the glass transitiontemperature of 315 K for the vinyl acetate homopolymer (cf. Ullmann'sEnzyclopädia of Industrial Chemistry, V C H Weinheim, Vol. A 21 (1992),page 169). In the course of simplified calculation of the glasstransition temperatures, it is possible to take into account only themain monomers (M1) and (M2) contributing to the formation of the phasesand to neglect the contributions of further monomers which result frommass fractions of less than 2% by weight, as long as the sum of the massfractions of these monomers does not exceed 4% by weight.

All monomers known to a person skilled in the art can be used as vinylesters of carboxylic acids having 1 to 18 carbon atoms (M1). Vinylesters of carboxylic acids having 1 to 8 carbon atoms are preferred,such as, for example, vinyl formate, vinyl acetate, vinyl propionate,vinyl isobutyrate, vinyl pivalate and vinyl 2-ethyhexylhexanoate; vinylesters of saturated, branched monocarboxylic acids having 9, 10 or 11carbon atoms in the acid radical (®Versatic acids); vinyl esters oflong-chain saturated and unsaturated fatty acids, such as, for example,vinyl laurate and vinyl stearate; vinyl esters of benzoic acid or ofp-tert-butylbenzoic acid and mixtures thereof. However, vinyl esters ofcarboxylic acids having 1 to 4 carbon atoms, mixtures of vinyl acetateand at least one versatic acid and mixtures of vinyl acetate and vinyllaurate are particularly preferred. Vinyl acetate is particularlypreferred.

Examples of monoethylenically unsaturated, optionallyhalogen-substituted hydrocarbons having 2 to 4 carbon atoms (M2), alsoreferred to below as monoolefins having 2 to 4 carbon atoms, are ethene,propene, 1-butene, 2-butene, isobutene, vinyl chloride and vinylidenechloride, ethene and mixtures of ethene and vinyl chloride beingpreferred. The amount of these monomers (M2) in the vinyl estercopolymer P is preferably less than 20% by weight, based on the totalmass of the monomers used for the preparation of the vinyl estercopolymer P.

Preferred monomer mixtures comprising the monomers M1 and M2 for thepreparation of the copolymers A and B according to the invention arevinyl acetate/vinyl chloride/ethene, vinyl acetate/vinyl laurate/ethene,vinyl acetate/vinyl laurate/ethene/vinyl chloride, vinyl acetate/vinylversatate/ethene/vinyl chloride, vinyl versatate/ethene/vinyl chloride,vinyl acetate/vinyl versatate/ethene and vinyl acetate/ethene, thecombination vinyl acetate/ethene being particularly preferred.

In the present application, ethylenically unsaturated, ionic monomers(M3) are preferably those ethylenically unsaturated monomers which havea water solubility of more than 50 g/l, preferably more than 80 g/l, at25° C. and 1 bar and which, in dilute aqueous solution at pH 2 and/or pH11, are present in a proportion of more than 50%, preferably more than80%, as an ionic compound or, at pH 2 and/or pH 11, are transformed intoan extent of more than 50%, preferably more than 80%, into an ioniccompound by protonation or deprotonation.

Suitable ethylenically unsaturated, ionic monomers (M3) are thosecompounds which carry at least one carboxylic acid, one sulfonic acid,one phosphoric acid or one phosphonic acid group directly neighboringthe double bond unit or a link to this via a spacer. The following maybe mentioned as examples: α,β-unsaturated C₃–C₈-monocarboxylic acids,α,β-unsaturated C₅–C₈-dicarboxylic acids and the anhydrides thereof, andmonoesters of α,β-unsaturated C₄–C₈-dicarboxylic acids.

Unsaturated monocarboxylic acids, such as, for example, acrylic acid and(meth)acrylic acid, and the anhydrides thereof; unsaturated dicarboxylicacids, such as, for example, maleic acid, fumaric acid, itaconic acidand citraconic acid and the monoesters thereof with C₁–C₁₂-alkanols,such as monomethyl maleate and mono-n-butyl maleate, are preferred.Further preferred, ethylenically unsaturated, ionic monomers (M3) areethylenically unsaturated sulfonic acids, such as, for example,vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid,2-acryloyloxy and 2-methacryloyloxyethanesulfonic acid, 2-acryloyloxy-and 3-methacryloyloxypropanesulfonic acid and vinylbenzenesulfonic acid,and ethylenically unsaturated phosphonic acids, such as, for example,vinylphosphonic acid.

Moreover, in addition to said acids, salts thereof may also be used,preferably the alkali metal salts thereof or the ammonium salts thereofand in particular the sodium salts thereof, such as, for example, sodiumsalts of vinylsulfonic acid and of 2-acrylamidopropanesulfonic acid.

Said ethylenically unsaturated, free acids are present in aqueoussolution at pH 11 predominantly in the form of their conjugated bases inanionic form and, like said salts, can be referred to as anionicmonomers.

Other suitable ethylenically unsaturated, ionic monomers (M3) aremonomers having a cationic functionality, such as, for example, monomersderived from quaternary ammonium groups. However, anionic monomers arepreferred.

A further object of the present invention was to overcome thedisadvantages of the known, heterogeneous vinyl ester dispersions, inparticular the insufficient blocking resistance of binder-rich coatingcompositions formulated with these dispersions (e.g. coatingcompositions having a PVC of less than the critical PVC), as well as theinsufficient abrasion resistance of coating compositions formulated withthese dispersions, having a low binder content and having highpigment/filler contents (e.g. coating compositions having a PVC greaterthan the critical PVC), and to provide novel universally applicablevinyl ester dispersions which are suitable both for the preparation ofbinder-rich coating systems having improved blocking resistance and forthe preparation of coating compositions having a low binder content andhigh pigment/filler contents, which have improved abrasion resistance.

This object is achieved if the vinyl ester copolymer P of the plasticmaterial dispersions according to the invention additionally contains,incorporated as copolymerized- units, up to 5% by weight, preferablyfrom 0.05 to 2% by weight and particularly preferably from 0.1 to 1.5%by weight, based on the total mass of the monomer used for thepreparation of the vinyl ester copolymer P, of at least one unsaturated,copolymerizable organosilicon compound (M4), also referred to below assilane compound.

Examples of said organosilicon compounds are monomers of the generalformula RSi(CH₃)₀₋₂(OR¹)₃₋₁, in which R has the meaning CH₂═CR²—(CH₂)₀₋₁or CH₂═CR²CO₂—(CH₂)₁₋₃, R¹ is a straight-chain or branched,unsubstituted or substituted alkyl radical having 3 to 12 C atoms, whichmay optionally be interrupted by an ether group, and R² is H or CH₃.

Organosilicon compounds of the formulae CH₂═CR²—(CH₂)₀₋₁Si(CH₃)₀₋₁(OR¹)₃₋₂ and CH₂═CR²—CO₂—(CH₂)₃Si (CH₃)₀₋₁(OR¹)₃₋₂, in which R¹is a branched or straight-chain alkyl radical having 1 to 8 C atoms andR² is H or CH₃, are preferred.

Particularly preferred organosilicon compounds arevinylmethyldimethoxysilane, vinylmethyldiethoxysilane,vinylmethyldi-n-propoxysilane, vinylmethyldiisopropoxy-silane,vinylmethyldi-n-butoxysilane, vinylmethyldi-sec-butoxysilane,vinylmethyldi-tert-butoxysilane,vinylmethyldi(2-methoxyisopropoxy)silane andvinylmethyldioctyloxysilane.

Organosilicon compounds of the formula CH₂═CR²—(CH₂)₀₋₁Si(OR¹)₃ andCH₂═CR²—CO₂—(CH₂)₃Si(OR¹)₃, in which R¹ is a branched or straight-chainalkyl radical having 1 to 4 C atoms and R² is H or CH₃, are particularlypreferred. Examples of these areγ-(meth)acryloyloxypropyltris(2-methoxyethoxy)silane,γ-(meth)acryloyloxypropyltrismethoxysilane,γ-(meth)acryl-oyloxypropyltrisethoxysilane,γ-(meth)acryloyloxypropyl-tris-n-propoxysilane,γ-(meth)acryloyloxypropyltris-isopropoxysilane,γ-(meth)acryloyloxypropyltrisbutoxy-silane,γ-acryloyloxypropyltris(2-methoxyethoxy)silane,γ-acryloyloxypropyltrismethoxysilane,γ-acryloyloxy-propyltrisethoxysilane,γ-acryloyloxypropyltris-n-propoxysilane,γ-acryloyloxypropyltrisisopropoxysilane,γ-acryloyloxypropyltrisbutoxysilane andvinyltris(2-methoxyethoxy)silane, vinyltrismethoxysilane,vinyl-trisethoxysilane, vinyltris-n-propoxysilane,vinyltris-isopropoxysilane and vinyltrisbutoxysilane. Said organosiliconcompounds can optionally also be used in the form of their (partial)hydrolysis products.

Furthermore, the vinyl ester copolymer P may contain, incorporated intothe copolymerized units, up to 5% by weight of ethylenicallyunsaturated, nonionic monomers (M5), based on the total mass of themonomers used for the preparation of the vinyl ester copolymer P. Theamount of these monomers (M5) is, however, preferably less than 2% byweight and particularly preferably less than 1% by weight.

In the present application, ethylenically unsaturated, nonionic monomers(M5) are preferably understood as meaning those ethylenicallyunsaturated compounds which have a water solubility of more than 50 g/l,preferably more than 80 g/l, at 25° C. and 1 bar and which are presentin dilute aqueous solution at pH 2 and pH 11 predominantly in nonionicform.

Preferred ethylenically unsaturated, nonionic monomers (M5) are both theamides of carboxylic acids mentioned in connection with theethylenically unsaturated, ionic monomers (M3), such as, for example,(meth)acrylamide and acrylamide, and water-soluble N-vinyllactams, suchas, for example, N-vinylpyrrolidone, and those compounds which containcovalently bonded polyethylene glycol units as ethylenically unsaturatedcompounds, such as, for example, polyethylene glycol mono- or diallylether and the esters of ethylenically unsaturated carboxylic acids withpolyalkylene glycols.

Moreover, the vinyl esters of copolymer P may contain, incorporated ascopolymerized units, up to 30% by weight, preferably up to 15% by weightand particularly preferably up to 10% by weight, of at least onefurther, ethylenically unsaturated monomer (M6), based on the total massof the monomers used for the preparation of the vinyl ester copolymer P.

Preferred further, ethylenically unsaturated monomers (M6) are inparticular the esters of ethylenically unsaturated C₃–C₈-mono- anddicarboxylic acids with C₁–C₈-, preferably C₁–C₁₂- and particularlypreferably C₁–C₈-alkanols or C₅–C₈-cycloalkanols. SuitableC₁–C₁₈-alkanols are, for example, methanol, ethanol, n-propanol,isopropanol, 1-butanol, 2-butanol, isobutanol tert-butanol, n-hexanol,2-ethylhexanol, lauryl alcohol and stearyl alcohol. Suitablecycloalkanols are, for example, cyclopentanol and cyclohexanol. Theesters of acrylic acid, of (meth)acrylic acid, of crotonic acid, ofmaleic acid, of itaconic acid, of citraconic acid and of fumaric acidare particularly preferred. The esters of acrylic acid and/or of(meth)acrylic acid, such as, for example, methyl (meth)acrylate, ethyl(meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate,isobutyl (meth)acrylate, 1-hexyl (meth)acrylate, tert-butyl(meth)acrylate and 2-ethylhexyl (meth)acrylate, and the esters offumaric acid and of maleic acid, such as, for example, dimethylfumarate, dimethyl maleate, di-n-butyl maleate, di-n-octyl maleate and2-ethylhexyl maleate, are particularly preferred. Said esters may alsobe unsubstituted or substituted by epoxy and/or hydroxyl groups.Moreover, suitable further ethylenically unsaturated monomers (M6) arenitriles of α,β-monoethylenically unsaturated C₃–C₈-carboxylic acids,such as, for example, acrylonitrile and (meth)acrylonitrile. ConjugatedC₄–C₈-dienes, such as, for example, 1,3-butadiene, isoprene andchloroprene, can also be used as monomers (M6).

A partial substitution of the vinyl ester by said compounds is carriedout as a rule in order to establish the properties of the homo- orcopolymers A and/or B, such as, for example, the hydrophobic/hydrophilicproperties.

Furthermore, those compounds which are known to improve the adhesionproperties and/or to act as crosslinking agents can also be used asfurther, ethylenically unsaturated monomers (M6).

The adhesion-improving monomers include both compounds which have anacetoacetoxy unit covalently bonded to the double bond system andcompounds having covalently bonded urea groups. The first-mentionedcompounds include in particular acetoacetoxyethyl (meth)acrylate andallyl acetoacetate. The compounds containing urea groups include, forexample, N-vinyl- and N-allylurea and derivatives of imidazolidin-2-one,such as, for example, N-vinyl- and N-allylimidazolid-2-one,N-vinyloxyethylimidazolidin-2-one,N-(2-(meth)acrylamidoethyl)imidazolidin-2-one,N-(2-methacryloyloxyethyl)imidazolidin-2-one andN-(2-(meth)acryloyloxyacetamidoethyl)imidazolidin-2-one, and furtheradhesion promoters known to a person skilled in the art and based onurea or imidazolidin-2-one. Diacetoneacrylamide in combination with asubsequent addition of adipic dihydrazide to the dispersion is alsosuitable for improving the adhesion. The adhesion-promoting monomerscan, if required, be used in amounts of 0.1 to 10% by weight, preferablyfrom 0.5 to 5% by weight, based on the total amount of the monomers usedfor the preparation of the vinyl ester copolymer P. In a preferredembodiment, however, the homo- or copolymers A and B contain none ofthese adhesion-promoting monomers incorporated as copolymerized units.

Both bifunctional and polyfunctional monomers can be used ascrosslinking monomers. Examples of these are diallyl phthalate, diallylmaleate, triallyl cyanurate, tetraallyloxyethane, divinylbenzene,butane-1,4-diol di(meth)acrylate, triethylene glycol di(meth)acrylate,divinyl adipate, allyl (meth)acrylate, vinyl crotonate,methylenebisacrylamide, hexanediol diacrylate, pentaerythritoldiacrylate and trimethylolpropane triacrylate. The crosslinking monomerscan, if required, be used in amounts of from 0.02 to 5% by weight,preferably from 0.02 to 1% by weight, based on the total mass of themonomers used for the preparation of the vinyl ester copolymer P. In apreferred embodiment, however, the homo- or copolymers A and B containnone of these crosslinking monomers incorporated with copolymerizedunits.

In addition to the vinyl ester copolymer P, the aqueous plastic materialdispersion according to the invention contains from 0 to 5% by weight,preferably from 0.1 to 4% by weight, particularly preferably from 1 to4% by weight and in particular from 2 to 4% by weight, based on thetotal mass of the monomers used for the preparation of the vinyl estercopolymer P, of ionic emulsifiers (S1). The ionic emulsifiers includeboth anionic and cationic emulsifiers, anionic emulsifiers and mixturesof anionic emulsifiers being particularly preferred.

The anionic emulsifiers include alkali metal and ammonium salts ofalkylsulfates (alkyl radical: C₆ to C₁₈), alkylphosphonates (alkylradical: C₆ to C₁₈), of sulfuric monoesters or phosphoric mono- anddiesters of ethoxylated alkanols (degree of ethoxylation: from 2 to 50,alkyl radical: C₆ to C₂₂) and ethoxylated alkylphenols (degree ofethoxylation: from 3 to 50, alkyl radical: C₄ to C₉), of alkanesulfonicacid (alkyl radical: C₁₂ to C₁₈), of alkylarylsulfonic acids (alkylradical: C₉ to C₁₈), of sulfosuccinic monoesters and sulfosuccinicdiesters of alkanols (alkyl radical: C₁₆ to C₂₂) and ethoxylatedalkanols (degree of ethoxylation: from 2 to 50, alkyl radical: C₆ toC₂₂), and nonethoxylated and ethoxylated alkylphenols (degree ofethoxylation: from 3 to 50, alkyl radical: C₄ to C₉). As a rule, theemulsifiers mentioned are used in the form of technical-grade mixtures,the data on a length of the alkyl radical and EO chain being based onthe respective maximum of the distribution occurring in the mixture.Examples of said emulsifier classes are ®Texapon K12 (sodiumlaurylsulfate from Cognis), ®Emulsogen EP (C₁₃–C₁₇-alkanesulfonate fromClariant), ®Maranil A 25 IS (sodium n-alkyl-(C₁₀–C₁₃)-benzenesulfonatefrom Cognis), ®Genapol liquid ZRO (sodium C₁₂/C₁₄-alkyl ether sulfatehaving 3 EO units from Clariant), ®Hostapal BVQ=4 (sodium salt of anonylphenol ether sulfate having 4 EO units from Clariant), ®Aerosol MA80 (sodium dihexylsulfosuccinate from Cyctec Industries), ®Aerosol A-268(disodium isodecylsulfosuccinate from Cytec Industries), ®Aerosol A-103(disodium salt of a monoester of sulfosuccinic acid with an ethoxylatednonylphenol from Cytec Industries).

Compounds of the General Formula I

in which R¹ and R² are hydrogen and C₄–C₂₄-alkyl, preferablyC₆–C₁₆-alkyl, and are not simultaneously hydrogen, and X and Y arealkali metal ions and/or ammonium ions, are furthermore suitable.Technical-grade mixtures which contain from 50 to 90% by weight of themonoalkylated product (for example Dowfax® 2A1 (R₁=C₁₂-alkyl; DOWChemical), are frequently also used in the case of these emulsifiers.The compounds are generally known, for example from U.S. Pat. No.4,269,749 and are commercially available.

In addition, the Gemini surfactants known to a person skilled in theart, as described, for example, in the article “Gemini-Tenside” [GeminiSurfactants] by F. M. Menger and J. S. Kelper (Angew. Chem. 2000, pages1980–1996) and the publications cited therein, are also particularlysuitable as ionic emulsifiers.

The cationic emulsifiers include, for example, alkylammonium acetates(alkyl radical: C₈ to C₁₂), quaternary compounds containing ammoniumgroups and pyridinium compounds.

When choosing the ionic emulsifiers, it should of course be ensured thatincompatibilities in the resulting plastic material dispersion, whichmay lead to coagulation, are ruled out. Anionic emulsifiers incombination with anionic monomers (M3) or cationic emulsifiers incombination with cationic monomers (M3) are therefore preferably used,the combination of anionic emulsifiers and anionic monomers beingparticularly preferred.

In addition to the ionic emulsifiers, the aqueous plastic materialdispersion according to the invention may also contain nonionicemulsifiers (S2). Suitable nonionic emulsifiers (S2) are araliphatic andaliphatic nonionic emulsifiers, for example ethoxylated mono-, di- andtrialkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C₄to C₉), ethoxylates of long-chain, branched or straight-chain alcohols(degree of ethoxylation: 3 to 50, alkyl radical: C₆ to C₃₆), andpolyethylene oxide/polypropylene oxide block copolymers. Ethoxylates oflong-chain, branched or straight-chain alkanols (alkyl radical: C₆ toC₂₂, average degree of ethoxylation: from 3 to 50) are preferred, andamong these those based on natural alcohols, Guerbet alcohols or oxoalcohols having a linear or branched C₁₂–C₁₈-alkyl radical and a degreeof ethoxylation of from 8 to 50 are particularly preferably used.

Further suitable emulsifiers are described in Houben-Weyl, Methoden derorganischen Chemie [Methods of Organic Chemistry], Volume XIV/1,Makromolekulare Stoffe [Macromolecular Substances], Georg-Thieme Verlag,Stuttgart, 1961, pages 192–208).

It is also possible to use both ionic and nonionic emulsifiers whichcontain one or more unsaturated double bond units as an additionalfunctionality and can be incorporated as ethylenically unsaturated,ionic monomers (M3) or as ethylenically unsaturated, nonionic monomers(M5) into the resulting polymer chains during the polymerizationprocess. These compounds referred to as copolymerizable emulsifiers(“surfmers”) are generally known to a person skilled in the art.Examples are to be found in a number of publications (e.g.: “Reactivesurfactants in heterophase polymerization” by A. Guyot et al. in ActaPolym. 1999, pages 57–66) and are commercially available (e.g.®Emulsogen R208 from Clariant or Trem LF 40 from Cognis).

Moreover, the total mass of ionic emulsifiers (S1) and ethylenicallyunsaturated, ionic monomers (M3) which are used for stabilizing theplastic material dispersion is at least 2% by weight, preferably atleast 3% by weight, based on the total mass of vinyl ester copolymer P.

In a particularly preferred embodiment of the present invention,nonionic components, i.e. nonionic emulsifiers (S2) and nonionicmonomers (M5), which can likewise be used for stabilizing the plasticmaterial dispersion, are generally dispensed with because the presenceof such nonionic components has a disadvantageous effect on the blockingresistance of binder-rich coatings produced using these plastic materialdispersions according to the invention.

If, however, for reasons relating to the stability in terms of colloidchemistry, it is not possible to dispense with such nonionic,stabilizing components, it is essential to ensure that the ratio of thetotal amount of ionic components (M3) and (S1) to the total amount ofnonionic components (M5) and (S2) used does not fall below the value 1,preferably the value 2 and particularly preferably the value 10.

The present invention also relates to methods for producing the aqueousplastic material dispersions according to the invention which are basedon vinyl ester copolymers.

The production of the aqueous plastic material dispersions according tothe invention which are based on vinyl ester copolymers P can beeffected, for example, by mixing two homo- or copolymers A and Bprepared separately.

However, the production can also be effected by a so-called stepwisepolymerization. Stepwise polymerization is generally understood asmeaning a procedure in which, in a 1st stage, the monomers of the 1ststage are polymerized by a free radical, aqueous emulsionpolymerization, preferably in the presence of seed latex, which ispreferably prepared in situ, and the monomers of the 2nd stage are thenpolymerized in the aqueous dispersion of the resulting polymer of the1st stage. If required, further polymerization stages can be effected.The comonomers of the 1st and 2nd stage differ regarding the type ofmonomers and/or with respect to the relative amounts of the monomers.Preferably, the type of monomers to be polymerized is the same for bothstages. There are then only differences with regard to the relativeamounts of the monomers.

When choosing the monomer composition of the individual stages, ingeneral a procedure is adopted in which a monomer composition whichleads to the formation of the homo- or copolymer B is chosen in thefirst stage and a corresponding monomer composition which leads to theformation of the homo- or copolymer A is polymerized in a further stage,preferably in the 2nd stage. However, it is also possible to proceed ina converse manner and to produce the homo- or copolymer B in thepresence of the previously prepared homo- or copolymer A and, ifrequired, further stages.

The vinyl ester copolymers P prepared by means of stepwisepolymerization comprise, independently of the detectable morphology, allcopolymers in which the homo- or copolymer components A and B have beenproduced by successive stages of the emulsion polymerization.

The monomer mixture for producing the homo- or copolymer A contains,based on the total amount of the monomers used for the preparation ofthe homo- or copolymer A, more than 50% by weight, preferably more than70% by weight, particularly preferably more than 80% by weight and inparticular from 80 to 95% by weight of monomers (M1) and less than 25%by weight, preferably from 5 to 20% by weight and particularlypreferably from 10 to 15% by weight of monoolefins having 2 to 4 C atoms(M2) preferably up to 10% by weight, particularly preferably up to 5% byweight and in particular up to 3% by weight of ionic monomers (M3), thecomposition of the monomer mixture being chosen so that the homo- orcopolymer polymerized separately with this monomer mixture has a glasstransition temperature in the range of from 0 to 20° C., preferably inthe range of from 0 to 15° C. and particularly preferably in the rangeof from 0 to 10° C.

The monomer mixture for producing the homo- or copolymer B contains,based on the total amount of the monomers used for the preparation ofthe homo- or copolymer B, more than 50% by weight, preferably more than70% by weight, particularly preferably more than 80% by weight and inparticular from 90 to 98% by weight of monomers (M1) and less than 25%by weight, preferably less than 20% by weight, particularly preferablyless than 0.1 to 10% by weight and in particular from 0.1 to 5% byweight of monoolefins having 2 to 4 C atoms (M2) and preferably up to10% by weight, particularly preferably up to 5% by weight and inparticular from 0.1 to 3% by weight of ionic monomers (M3), thecomposition of the monomer mixture being chosen so that the homo- orcopolymer polymerized separately with this monomer mixture has a glasstransition temperature in the range from 20 to 50° C., preferably in therange of from 25 to 45° C. and particularly preferably in the range offrom 30 to 43° C.

In addition, when choosing the monomer compositions of the two homo- orcopolymers A and B of the heterogeneous vinyl ester copolymer P, itshould be ensured that their glass transition temperatures differ bymore than 10 K, preferably by more than 15 K and particularly preferablyby more than 20 K.

When choosing the monomer compositions, it should moreover be ensuredthat, based on the total amount of the monomers used for the preparationof the copolymer P, less than 20% by weight, preferably from 0.1 to 20%by weight and particularly preferably from 0.1 to 15% by weight, ofethylenically unsaturated monoolefins having 2 to 4 carbon atoms (M2)are used.

In particular embodiments, it may be necessary to carry out theindividual polymerization stages under different polymerizationpressures owing to the different amounts of monoolefins (M2) which arepresent in the gaseous state of aggregation under the reactionconditions. In these cases, the pressure which is generated by meteringthe gaseous monoolefins (M2) is preferably between 0 and 10 bar,particularly preferably between 2 and 10 bar, during the polymerizationof the monomer composition leading to copolymer B and preferably between10 and 120 bar, particularly preferably between 20 and 60 bar, duringthe polymerization of the monomer composition leading to copolymer A.

Surprisingly, it was found that a polymerization of the individualstages up to monomer contents of <0.3%, as usually carried out forgenerating separate polymer phases, is not necessary for the preparationof the vinyl ester copolymers, P, copolymer A being produced in thepresence of copolymer B.

In a particularly preferred embodiment, it is therefore sufficient if,after production of the copolymer B, the concentration of the monomercomponent(s) M2 which are present in gaseous form under the reactionconditions is gradually increased over an appropriate time interval forcontinuous metering of liquid monomer components, for generating thecopolymer A (pressure increase). This method is distinguished bysubstantially reduced reactor utilization times compared with themethods usually used.

The polymerization is generally carried out at temperatures in the rangeof from 20 to 120° C., preferably in the range of from 40 to 95° C. andparticularly preferably in the range of from 50 to 90° C.

The production of the aqueous plastic material dispersions according tothe invention which are based on vinyl ester copolymers is preferablyeffected by free radical, aqueous emulsion polymerization of saidmonomers in the presence of at least one free radical polymerizationinitiator and at least one surface-active substance.

Suitable free radical polymerization initiators are all known initiatorswhich are capable of initiating a free radical, aqueous emulsionpolymerization. They may be both peroxides, such as, for example, alkalimetal peroxodisulfates, and azo compounds. So-called redox initiators,which are composed of at least one organic and/or inorganic reducingagent and at least one peroxide and/or hydroperoxide, such as, forexample, tert-butyl hydroperoxide with sulfur compounds, such as, forexample, the sodium salts of hydroxymethanesulfinic acid, sodiumsulfite, sodium disulfite, sodium thiosulfate and acetone bisulfateadducts, or hydrogen peroxide with ascorbic acid, can also be used aspolymerization initiators. Combined systems which contain a small amountof a metal compound which is soluble in the polymerization medium andwhose metallic component can occur in a plurality of valency states,such as, for example, ascorbic acid/iron(II) sulfate/hydrogen peroxide,can also be used, the sodium salt of hydroxmethylsulfic acid, acetonebisulfite adduct, sodium sulfite, sodium hydrogen sulfite or sodiumbisulfite also frequently being used instead of ascorbic acid, andorganic peroxides, such as, for example, tert-butyl hydroperoxide oralkali metal peroxodisulfates and/or ammonium peroxodisulfate, alsofrequently being used instead of hydrogen peroxide. Instead of saidacetone bisulfite adduct, further bisulfite adducts known to a personskilled in the art, as described, for example, in EP-A-0 778 290 and inthe literature cited therein, can also be used. Further preferredinitiators are peroxodisulfates, such as, for example, sodiumperoxodisulfate. The amount of the free radical initiator systems usedis preferably from 0.05 to 2.0% by weight, based on the total amount ofthe monomers to be polymerized.

Protective colloids and the ionic and, if required, the nonionicemulsifiers S1 and S2 described above, whose relative molecular weights,in contrast to the protective colloids, are less than 2 000 g/mol, areusually used as surface-active substances in the emulsionpolymerization.

The surface-active substances are usually used in amounts of up to 10%by weight, preferably from 0.5 to 7% by weight and particularlypreferably from 1 to 6% by weight, based on the monomers to bepolymerized.

Suitable protective colloids are, for example, polyvinyl alcohols,starch derivatives and cellulose derivatives and vinylpyrrolidone,polyvinyl alcohols and cellulose derivatives, such as, for example,hydroxyethylcelluloses, being preferred. A detailed description offurther, suitable protective colloids is to be found in Houben-Weyl,Methoden der organischen Chemie [Methods of Organic Chemistry], VolumeXIV/1, Makromolekulare Stoffe [Macromolecular Substances], Georg-ThiemeVerlag, Stuttgart 1961, pages 411 to 420.

The molecular weight of the vinyl ester copolymers can be established byadding small amounts of one or more substances which regulate themolecular weight. These so-called “regulators” are generally used in anamount of up to 2% by weight, based on the monomers to be polymerized.All substances known to a person skilled in the art can be used as“regulators”. For example, organic thio compounds, silanes, allylalcohols and aldehydes are preferred.

The emulsion polymerization is usually effected by a batch procedure,preferably by a semicontinuous method. In semicontinuous methods, themain amount, i.e. at least 70%, preferably at least 90%, of the monomersto be polymerized is fed continuously, including the stepwise orgradient procedure, to the polymerization batch. This procedure is alsoreferred to as the monomer feed method, monomer feed being understood asmeaning the metering of gaseous monomers, liquid monomer mixtures,monomer solutions or in particular aqueous monomer emulsions. Themetering of the individual monomers can be effected by separate feeds.

In addition to the seed-free production method, the emulsionpolymerization can also be effected by the seed latex method or in thepresence of seed latices produced in situ, for establishing a definedpolymer particle size. Such methods are known and are described indetail in a multiplicity of patent applications (e.g. EP-A-0 040 419 andEP-A-0 567 812) and publications (“Encyclopedia of Polymer Science andTechnology”, Vol. 5, John Wiley & Sons Inc., New York 1966, page 847).

After the actual polymerization reaction, it may be desirable and/ornecessary substantially to free the aqueous plastic material dispersionsaccording to the invention from odorous substances, such as, forexample, residual monomers and other volatile, organic components. Thiscan be achieved in a manner known per se, for example physically bydistillative removal (in particular by steam distillation) or bystripping with an inert gas. Furthermore, the reduction of the residualmonomer may also be effected chemically by free radicalpostpolymerization, in particular with the action of redox initiatorsystems, as described, for example, in DE-A-44 35 423. Thepostpolymerization using a redox initiator system comprising at leastone organic peroxide and one organic and/or inorganic sulfite ispreferred. A combination of physical and chemical methods isparticularly preferred, a reduction of the residual monomer content bychemical postpolymerization being followed by further reduction of theresidual monomer content by means of physical methods to, preferably, <1000 ppm, particularly preferably <500 ppm, in particular <100.

The aqueous plastic material dispersions according to the inventionwhich are based on vinyl ester copolymers are used, for example, asbinders in pigment-containing, aqueous formulations which serve forcoating substrates. These include, for example, synthetic resin-boundrenders, tile adhesives, coating materials, such as, for example,emulsion paints, emulsion finishes and glazes, joint sealing compoundsand sealing compounds, preferably for porous components, but also papercoating slips.

The aqueous plastic material dispersions can, however, also be useddirectly or after addition of rheology-modifying additives and/or othercomponents as aqueous formulations for coating substrates. Such aqueousformulations are, for example, primers, clear finishes or food coatingswhich protect food, such as, for example, cheese or meat-containingpreparations, from harmful environmental influences and/or drying out.

The present invention therefore furthermore relates to aqueousformulations containing the aqueous plastic material dispersionaccording to the invention which is based on vinyl ester copolymers. Apreferred embodiment of the aqueous formulation are pigment-containing,aqueous formulations.

These preferred, pigment-containing formulations, particularlypreferably emulsion paints, contain in general from 30 to 75% by weight,preferably from 40 to 65% by weight, of nonvolatile components. Theseare understood as meaning all components of the formulation except forwater, with at least the total amount of the solid binder, filler,pigment, plasticizer and polymeric assistant.

Of the nonvolatile components, preferably

-   -   a) from 3 to 90% by weight, particularly preferably from 10 to        60% by weight, are accounted for by the solid binder, i.e. the        vinyl ester copolymer P,    -   b) from 5 to 85% by weight, particularly preferably from 10 to        60% by weight, are accounted for by at least one inorganic        pigment,    -   c) from 0 to 85% by weight, particularly preferably from 20 to        70% by weight, are accounted for by inorganic fillers and    -   d) from 0.1 to 40% by weight, particularly preferably from 0.5        to 15% by weight, are accounted for by conventional assistants.

Solvent- and plasticizer-free, aqueous formulations are particularlypreferred.

The pigment volume concentration (PVC) of the pigment-containing,aqueous formulations according to the invention is in general above 5%,preferably in the range of from 10 to 90%. In particularly preferredembodiments, the PVCs are either in the range of from 10 to 45% or inthe range from 60 to 90%, in particular from 70 to 90%.

Pigments which may be used are all pigments known to a person skilled inthe art for said intended use. Preferred pigments for the aqueousformulations according to the invention, preferably for emulsion paints,are, for example, titanium dioxide, preferably in the form of rutile,barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimonytrioxide and lithopone (zinc sulfide and barium sulfate). However, theaqueous formulations can also contain colored pigments, for example ironoxides, carbon black, graphite, luminescent pigments, zinc yellow, zincgreen, ultramarine, manganese black, antimony black, manganese violet,Paris blue or Schweinfurt green. In addition to the inorganic pigments,the formulations according to the invention may also contain organiccolored pigments, for example sepia, gamboge, Kasset brown, toluidinered, para red, Hansa yellow, indigo, azo dyes, anthraquinoid andindigoid dyes and dioxazine, quinacridone, phthalocyanine, isoindolinoneand metal complex pigments.

Fillers which may be used are all fillers known to a person skilled inthe art for said intended use. Preferred fillers are aluminosilicates,such as, for example, feldspars, silicates, such as, for example,kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as,for example, calcium carbonate, for example in the form of calcite orchalk, magnesium carbonate, dolomite, alkaline earth metal sulfates,such as, for example, calcium sulfate, and silica. The fillers can beused either as individual components or as filler mixtures. Fillermixtures, such as, for example, calcium carbonate/kaolin and calciumcarbonate/talc, are preferred in practice. Synthetic resin-bound rendersmay also contain relatively coarse additives, such as sands or sandstonegranules.

In general, finely divided fillers are preferred in emulsion paints. Inorder to increase the hiding power and to save white pigments, finelydivided fillers, such as, for example, precipitated calcium carbonate ormixtures of different calcium carbonates having different particlesizes, are frequently used in emulsion paints. Mixtures of coloredpigments and fillers are preferably used for adjusting the hiding powerof the hue and the depth of color.

The conventional assistants include wetting agents or dispersants, suchas sodium, potassium or ammonium polyphosphates, alkali metal andammonium salts of polyacrylic acids and of polymaleic acid,polyphosphonates, such as sodium 1-hydroxyethane-1,1-diphosphonate, andnaphthalenesulfonic acid salts, in particular the sodium salts thereof.In addition, suitable amino alcohols, such as, for example,2-amino-2-methylpropanol, may be used as dispersants. The dispersants orwetting agents are preferably used in an amount of from 0.1 to 2% byweight, based on the total weight of the emulsion paint.

Furthermore, the assistants may also comprise thickeners, for examplecellulose derivatives, such as methylcellulose, hydroxyethylcelluloseand carboxymethylcellulose, and furthermore casein, gum arabic,tragacanth gum, starch, sodium alginate, polyvinyl alcohol,polyvinylpyrrolidone, sodium polyacrylates, water-soluble copolymersbased on acrylic and (meth)acrylic acid, such as acrylic acid/acrylamideand (meth)acrylic acid/acrylic ester copolymers and so-calledassociative thickeners, such as styrene/maleic anhydride polymers orpreferably hydrophobically modified polyetherurethanes (HEUR) known to aperson skilled in the art, hydrophobically modified acrylic acidcopolymers (HASE) and polyetherpolyols.

Inorganic thickeners, such as, for example, bentonites or hectorite, mayalso be used.

The thickeners are preferably used in amounts of from 0.1 to 3% byweight, particularly preferably from 0.1 to 1% by weight, based on thetotal weight of the aqueous formulation.

The aqueous formulations according to the invention may also containcrosslinking additives. Such additives may be: aromatic ketones, suchas, for example, alkyl phenyl ketones, which optionally have one or moresubstituents on the phenyl ring, or benzophenone or substitutedbenzophenones as photoinitiators. Photoinitiators suitable for thispurpose are disclosed, for example, in DE-A-38 27 975 and EP-A-0 417568. Suitable, crosslinking compounds are also water-soluble compoundshaving at least two amino groups, for example dihydrazides of aliphaticdicarboxylic acids, as disclosed, for example, in DE-A-39 01 073, if thevinyl ester copolymer p contains, incorporated as copolymerized units,monomers containing carbonyl groups.

In addition, waxes based on paraffins and polyethylene, and dullingagents, antifoams, preservatives and water repellents, biocides, fibersand further additives known to a person skilled in the art may be usedas assistants in the aqueous formulations according to the invention.

The dispersions according to the invention can be used to prepare notonly solvent- and plasticizer-free formulations but of course alsocoating systems which contain solvents and/or plasticizers as filmformation assistants. Film formation assistants are generally known to aperson skilled in the art and can usually be used in amounts of from 0.1to 20% by weight, based on the vinyl ester copolymer P contained in theformulation, so that the aqueous formulation has a minimum filmformation temperature of less than 15° C., preferably in the range offrom 0 to 10° C. The use of these film formation assistants is, however,not necessary in view of the advantageous properties of the plasticmaterial dispersions according to the invention. In a preferredembodiment, the aqueous formulations according to the inventiontherefore contain no film formation assistant.

The aqueous formulations according to the invention are stable fluidsystems which can be used for coating a multiplicity of substrates.Consequently, the present invention also relates to methods for coatingsubstrates and the coating materials themselves. Suitable substratesare, for example, wood, concrete, metal, glass, ceramics, plastics,renders, wallpapers, paper, coated, primed or weathered substrates. Theapplication of the formulation to the substrate to be coated is effectedin a manner dependent on the nature of the formulation. Depending on theviscosity and the pigment content of the formulation and on thesubstrate, the application can be effected by means of roll-coating,brushing or knife coating or as a spray.

The advantageous properties of the vinyl ester copolymer P as a bindercompared with vinyl ester copolymers from the prior art, especially theimproved blocking resistance in binder-rich coating compositions, isparticularly evident in the case of pigment-containing formulationshaving a PVC of <45%, preferably from 10 to 45%.

In addition, those vinyl ester copolymers P which contain organosiliconcompounds incorporated as copolymerized units not only improve blockingresistance in binder-rich coating compositions having a PVC of less than45% but also further advantageous properties, such as improved wetabrasion resistance, in aqueous formulations having a PVC of >60%.Improved wet abrasion resistance, i.e. improved mechanical stability ofthe coating to abrasive influences in the moist state, is advantageousfor the wet cleaning resistance of the coatings as well as in outdoorapplications, for example for stability to weathering, and ensures thatthe coatings are washable. Thus, the advantages of the vinyl estercopolymers P according to the invention which contain organosiliconcompounds are particularly evident in formulations which have a PVC inthe range of from 10 to 90%, for example in the case of a PVC in therange of from 10 to 45% or in the case of a PVC in the range of from 60to 90%, in particular from 70 to 90%.

The invention is described in more detail below with reference toworking examples, but without being restricted thereby in any way.

I. Production and Characterization of Plastic Material DispersionsAccording to the Invention

The dispersions produced in the examples and comparative examples areproduced in a 70 l pressure-resistant autoclave having jacket coolingand a permissible pressure range of up to 160 bar. Parts and percentagesused in the examples below are based on weight, unless stated otherwise.

The viscosities of the dispersions are determined using a Haakerotational viscometer (Rheomat® VT 500) at room temperature and a sheargradient of 17.93 s⁻¹.

The mean particle size and the particle size distribution are determinedby laser and white light aerosol spectroscopy. The stated particle sizescorrespond to the particle diameter after drying.

The amounts of residual monomers stated in the examples are determinedby gas chromatography (GC).

The determination of the minimum film formation temperature (MFT) of thepolymer dispersion is effected on the basis of Ullmans Enzyclopädie dertechnischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 4thedition, Vol. 19, V C H Weinheim 1980, page 17. The measuring apparatusused is a so-called film formation bench which consists of a metal plateto which a temperature gradient is applied and on which the temperaturesensors are mounted at various points for temperature calibration, thetemperature gradient being chosen so that one end of the film formationbench has a temperature above the MFT to be expected and the other endhas a temperature below the MFT to be expected. The aqueous polymerdispersion is then applied to the film formation bench. In those regionsof the film formation bench whose temperature is above the MFT, a clearfilm forms on drying, whereas tears occur in the cooler regions and, ateven lower temperatures, a white powder forms. On the basis of the knowntemperature profile of the plate, the MFT is determined visually as thetemperature at which a tear-free film is first present.

The glass transition temperature of the individual polymerization stagesis calculated approximately according to the Fox equation, taking intoaccount the main monomers. The glass transition temperatures of thehomopolymers corresponding to the individual monomers are used as abasis for calculation, as described in Ullmann's Enzyclopädia ofIndustrial Chemistry, VCH Weinheim, Vol. A 21 (1992), page 169, or inBrandrup, E. H. Immergut Polymer Handbook, 3^(rd) ed, J. Wiley, New York1989. A glass transition temperature of the homopolymer of 148 K istaken for ethene (cf. Brandrup, E. H. Immergut Polymer Handbook, 3^(rd)ed, J. Wiley, New York 1989, page VI/214) and a glass transitiontemperature of the homopolymer of 315 K is taken for vinyl acetate (cf.Ullmann's Enzyclopädia of Industrial Chemistry, V C H Weinheim, Vol. A21 (1992), page 169).

The data on the ethene content are based on the relative proportion byweight of ethene in the monomer units in the copolymer P.

COMPARATIVE EXAMPLE A1

Polymerization Stage I:

A solution (initially introduced mixture) consisting of the followingcomponents is introduced into a 70 l pressure-resistant reaction vesselhaving a temperature-regulating means, stirrer, metering pumps and ametering means for gaseous ethene (mass flow rate measurement):

 8 060 g of water  88.55 g of sodium acetate  594.5 g of 30% strengthsodium ethenesulfonate solution in water  70.45 g of sodiumlaurylsulfate (® Texapon K12 granules, Cognis)  5 284 g of 20% strengthsolution of a nonylphenol ethoxylate having 30 ethylene oxide units(® Arkopal N300, Clariant) in water  34.87 g of a 1% strength solutionof Fe(II) SO₄.7H₂O in water 14 240 g of a 5% strength solution ofhydroxyethylcellulose in water (HEC solution) (viscosity of the 2%strength by weight aqueous solution 350 mPa · s)

The pH of the initially introduced component is 7.2. The apparatus isfreed of atmospheric oxygen by evacuating twice and flushing withnitrogen. It is evacuated a third time and a total of 350 g of etheneare forced into the apparatus, the internal pressure of the vessel beingabout 7 bar after this amount of ethene has been metered in. Thereafter,the ethene feed is closed and 3 170 g of vinyl acetate and 2.82 g of®Rongalit C (BASF), dissolved in 208 g of water, are metered in.Thereafter, the internal temperature is increased to 60° C. On reachingan internal temperature of 50° C., a mixture of 4.0 g of an aqueous 70%strength tert-butyl hydroperoxide solution and 208 g of water is meteredin, and cooling is effected to remove the heat of reaction. On reachingan internal temperature of 60° C., 7 133 g of vinyl acetate are meteredin in the course of 90 minutes, and a solution of 9.1 g of ®Rongalit Cin 669 g of water and a mixture of 12.9 g of an aqueous 70% strengthtert-butyl hydroperoxide solution and 669 g of water in the course of130 minutes. The internal temperature is kept at 60° C. over the entiremetering time. A dispersion sample which was taken after the end of themeterings of the initiator components has a residual vinyl acetatecontent of <0.3% and a solids content of 31.2%.

Polymerization Stage 2:

After the end of the metering of the initiator solutions of the firststage, the ethene valve is opened and the internal pressure of thevessel increased to 40 bar at an internal temperature of 60° C. bymetering in ethene. After the internal pressure of the vessel hasreached 40 bar, 21 400 g of vinyl acetate and a solution of 18.8 g of®Rongalit C in 1 389 g of water and a mixture of 27.0 g of an aqueous70% strength solution of tert-butyl hydroperoxide solution and 1 389 gof water are metered in at an internal temperature of 60° C. in thecourse of 270 minutes. The ethene feed remains open at an internalpressure of 40 bar until a further 3 172 g of ethene have been meteredin. After the end of all meterings, a solution of 35.7 g of sodiumperoxodisulfate in 832 g of water is added, the internal temperature isincreased to 80° C. and, after the end of the reaction, cooling iseffected for a further hour. The internal pressure of the vessel aftercooling to 30° C. is 0.15 bar.

EXAMPLE A2

The dispersion is produced analogously to the production of thedispersion described under example A1. In contrast to this, a solutionof the following components was used as the initially introducedmixture:

10 580 g of water  88.55 g of sodium acetate  594.5 g of 30% strengthsodium ethenesulfonate solution in water  2 439 g of a 30% strengthsolution of a sodium C₁₃–C₁₇- alkanesulfonate in water (® Emulsogen EP,Clariant)  34.87 g of a 1% strength solution of Fe(II) SO₄.7H₂O in water14 240 g of a 5% strength solution of hydroxyethylcellulose in water(HEC solution) (viscosity of the 2% strength by weight aqueous solution350 mPa · s)

The pH of the initially introduced mixture is 7.3.

A dispersion sample which is taken at the end of the polymerizationstage 1 has a residual vinyl acetate content of <0.3% and a solidscontent of 30.8%. The internal pressure of the vessel after the end ofthe reaction and cooling to 30° C. is 0.24 bar.

EXAMPLE A3

A solution consisting of the following components is introduced as aninitially introduced mixture into a 70 l pressure-resistant reactionvessel having a temperature-regulating means, stirrer, metering pumpsand a metering means for gaseous ethene:

10 955 g of water 88.55 g of sodium acetate 594.5 g of 30% strengthsodium ethenesulfonate solution in water 2 439 g of a 30% strengthsolution of a sodium C₁₃—C₁₇- alkanesulfonate in water (® Emulsogen EP,Clariant) 34.87 g of a 1% strength solution of Fe(II) SO₄.7H₂O in water14 240 g of a 5% strength solution of hydroxyethylcellulose in water(HEC solution) (viscosity of the 2% strength by weight aqueous solution350 mPa · s)

The pH of the initially introduced mixture is 7.3. The apparatus is thenfreed of atmospheric oxygen by evacuating twice and flushing withnitrogen. It is evacuated a third time and a total of 350 g of etheneare forced into the apparatus (beginning of polymerization stage 1), theinternal pressure of the vessel being about 7 bar after this amount ofethene has been metered in. Thereafter, the ethene feed is closed and3170 g of vinyl acetate and 2.82 g of ®Rongalit C, dissolved in 208 g ofwater, are metered in. The internal temperature is then increased to 60°C. On reaching an internal temperature of 50° C., a solution of 4.0 g ofan aqueous 70% strength tert-butyl hydroperoxide solution in 208 g ofwater is metered in and cooling is effected to remove the heat ofreaction. When an internal temperature of 60° C. has been reached, 28532 g of vinyl acetate and 25.4 g of ®Rongalit C, dissolved in 1 871 gof water, and a mixture of 36.2 g of an aqueous 70% strength tert-butylhydroperoxide solution and 1 871 g of water are metered in in the courseof 360 minutes. The internal temperature is kept at 60° C. over theentire metering time. 90 minutes after the beginning of metering, theethene feed is opened again (beginning of polymerization stage 2) andthe internal pressure of the vessel is increased to 40 bar by meteringin ethene, the ethene feed remaining opened at this internal pressureuntil a further 3 172 g of ethene have been metered in. A dispersionsample taken after 90 minutes has a residual vinyl acetate content of0.89% and a solids content of 30.8%. After all meterings have beenterminated, a solution of 35.7 g of sodium peroxodisulfate in 832 g ofwater is added, the internal temperature is increased to 80° C. and,after the end of the reaction, cooling is effected after a further hour.The internal pressure of the vessel after cooling to 30° C. is 0.25 bar.

EXAMPLE A4

The dispersion is produced analogously to the production of thedispersion described under example A3. In contrast, a solutionconsisting of the following components is used as the initiallyintroduced mixture:

12 663 g of water 88.55 g of sodium acetate 594.5 g of 30% strengthsodium ethenesulfonate solution in water 731.7 g of sodium laurylsulfate(® Texapon K12 granules, Cognis) 34.87 g of a 1% strength solution ofFe(II) SO₄.7H₂O in water 14 240 g of a 5% strength solution ofhydroxyethylcellulose in water (HEC solution) (viscosity of the 2%strength aqueous solution 350 mPa · s)

The pH of the initially introduced mixture is 10.2. The internalpressure of the vessel after the end of the reaction and cooling to 30°C. is 0.24 bar.

EXAMPLE A5

The dispersion is produced analogously to the production of thedispersion described under example A3. In contrast, a solutionconsisting of the following components is used as the initiallyintroduced mixture:

10 781 g of water 88.55 g of sodium acetate 594.5 g of 30% strengthsodium ethenesulfonate solution in water 2 613 g of a 28% strengthsolution of a sodium C₁₂/C₁₄- alkyl ether sulfate having 3 ethyleneoxide units in water (® Genapol ZRO liquid, Clariant) 34.87 g of a 1%strength solution of Fe(II) SO₄.7H₂O in water 14 240 g of a 5% strengthsolution of hydroxyethylcellulose in water (HEC solution) (viscosity ofthe 2% strength aqueous solution 350 mPa · s)

The pH of the initially introduced mixture is 10.3. The internalpressure of the vessel after the end of the reaction and cooling to 30°C. is 1.6 bar.

EXAMPLE A6

The dispersion is produced analogously to the production of thedispersion described under example A2. In contrast, instead of theamounts by weight of vinyl acetate stated in example A2 (31 703 galtogether), in each case identical amounts by weight of a mixture of99.555% by weight of vinyl acetate and 0.445% by weight ofγ-methacryloyloxypropyltrimethoxysilane (altogether 31 562 g of vinylacetate and 141 g of γ-methacryloyloxypropyltrimethoxysilane) aremetered in. A dispersion sample which is taken at the end ofpolymerization stage 1 has a residual vinyl acetate content of <0.3% anda solids content of 29.8%. The internal pressure of the vessel after theend of the reaction and cooling to 30° C. is 0.7 bar.

EXAMPLE A7

The dispersion is produced analogously to the production of thedispersion described under example A3. In contrast, instead of theamounts by weight of vinyl acetate stated in example 3 (31 703 galtogether), in each case identical amounts by weight of a mixture of99.555% by weight of vinyl acetate and 0.445% by weight ofγ-methacryloyloxypropyl-trimethoxysilane (altogether 31 562 g of vinylacetate and 141 g of γ-methacryloyloxypropyltrimethoxysilane) aremetered in. A dispersion sample which is taken at the end ofpolymerization stage 1 has a residual vinyl acetate content of 0.9% anda solids content of 28.5%. The internal pressure of the vessel after theend of the reaction and cooling to 30° C. is 0.35 bar.

EXAMPLE A8

The dispersion is produced analogously to the production of thedispersion described under example A4. In contrast, instead of theamounts by weight of vinyl acetate stated in example A4 (31 703 galtogether), in each case identical amounts by weight of a mixture of99.555% by weight of vinyl acetate and 0.445% by weight ofγ-methacryloyloxypropyl-trimethoxysilane (altogether 31 562 g of vinylacetate and 141 g of γ-methacryloyloxypropyltrimethoxysilane) aremetered in. The internal pressure of the vessel after the end of thereaction and cooling to 30° C. is 2.0 bar.

In table 1 below, the monomer compositions used for the production ofthe dispersions for the amounts by weight of emulsifiers used inexamples A1 to A8, and the monomer compositions used for the productionof the individual copolymerization stages are summarized.

TABLE 1 Composition of the dispersions from examples A1 to A8 ExampleA1^(a)) A2 A3 A4 A5 A6 A7 A8 Monomer composition: copolymer P (% byweight^(b))) Vinyl ester (M1) 89.5 89.5 89.5 89.5 89.5 89.1 89.1 89.1Monoolefins (M2) 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Ionic monomers(M3) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Silane monomers (M4) — — — — — 0.40.4 0.4 Ratio of copolymer 69.4/ 69.4/ 69.4/ 69.4/ 69.4/ 69.4/ 69.4/69.4/ A/B 30.6 30.6 30.6 30.6 30.6 30.6 30.6 30.6 Emulsifiers (% byweight^(b))) Ionic emulsifiers (S1) 0.2 2.1 2.1 2.1 2.1 2.1 2.1 2.1Nonionic 3.0 — — — — — — — emulsifiers (S2) Monomer composition:copolymer A (% by weight^(c))) Vinyl ester (M1) 87.1 87.1 87.1 87.1 87.186.7 87.6 86.7 Monoolefins (M2) 12.9 12.9 12.9 12.9 12.9 12.9 12.9 12.9Silane monomers (M4) — — — — — 0.4 0.4 0.4 Tg (A) [° C.] about 2 about 2about 2 about 2 about 2 about 2 about 2 about 2 Monomer composition:copolymer B (% by weight^(d))) Vinyl ester (M1) 95.1 95.1 95.1 95.1 95.194.7 94.7 94.7 Monoolefins (M2) 3.2 3.2 3.2 3.2 3.2 3.2 3.2 3.2 Ionicmonomers (M3) 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 Silane monomers (M4) — — —— — 0.4 0.4 0.4 Tg (B) [° C.] about about about about about about aboutabout 31 31 31 31 31 31 31 31 ^(a))Comparative example; ^(b))% by weightare based on the total mass of the monomers used for the preparation ofthe copolymers P; ^(c))% by weight are based on the total mass of themonomers used for the preparation of the copolymer A; ^(d))% by weightare based on the total mass of the monomers used for the preparation ofthe copolymer B; ^(e))glass transition temperatures of thepolymerization stages (calculated according to Fox)

The characteristic data of the dispersions from examples A1 to A8 and ofa commercial, homogeneous vinyl acetate/ethene copolymer dispersion V2(Tg: 14° C., DSC analysis, heating rate 20 K/min) are contained in table2.

TABLE 2 Characteristic data of the dispersions from examples A1 to A8Example A1^(a)) A2 A3 A4 A5 A6 A7 A8 V2^(a)) Solids [%] 54.0 53.6 53.753.9 53.3 53.8 53.3 53.4 53.0 pH 4.9 4.9 4.9 4.9 4.8 4.9 4.9 4.6 4.4Particle 100–500 100–500 100–500 100–500 100–500 100–500 100–500 100–500100–500 size distribution [nm] Weight 218 301 266 273 174 328 258 302214 average particle diameter [nm] Viscosity 1.31 0.312 0.380 0.475 1.120.380 0.362 0.340 1.04 [Pa · s] Residual <0.15 <0.15 <0.15 <0.15 <0.15<0.15 <0.15 <0.15 <0.15 monomer content (GC) [%] MFT [° C.] 3 3 <0 4 <02 <0 6 <0 ^(a))Comparative example; ^(b))minimum film formationtemperature

The performance characteristics (surface tack) of coating materialswhich are obtained after drying of the pure dispersions A1 to A8 and V2are summarized in table 3.

The results of testing the performance characteristics of the coatingmaterials according to the invention in table 3, which are obtainedafter drying the pure dispersions from examples A2 to A8, clearly showthat, compared with a vinyl acetate/ethene copolymer dispersion knownfrom the prior art and according to example A1 and a commercial,homogeneous vinyl acetate/ethene copolymer dispersion V2, substantiallylower surface tack of the dried coating can be achieved by theheterogeneity according to the invention and predominant stabilizationwith ionic components.

TABLE 3 Surface tack of dried dispersion films Stabilization of thedispersion Σ M₅ ^(a)) and Σ M₃ ^(c)) and Dispersion S₂ ^(b)) [%]^(e)) S₁^(d)) [%]^(e)) Surface tack A1 (V1¹⁾) 3 0.7 6 A1 0 2.6 3 A3 0 2.6 4 A4 02.6 3 A5 0 2.6 1 A6 0 2.6 3 A7 0 2.6 3 A8 0 2.6 1 V2⁹⁾ —^(h)) —^(h)) 6^(a))M₅: Nonionic monomers; ^(b))S₂: non-ionic emulsifiers; ^(c))M₃:Ionic monomers; ^(d))S₁: Ionic emulsifiers; ^(e))Stated percentages arebased on the total amount of the monomers used for the production of thedispersion; ^(f))Comparative dispersion 1; ^(g))Comparative dispersion2: commercial, homogeneous vinyl acetate/ethene copolymer dispersion;^(h))not specified.II. Preparation of the Pigment-containing Formulations According to theInvention

II.1. Solvent-Free Dispersion Finish Having a PVC of 16.8%; Formulation(I) (Comparative Examples B1 and B9), Examples B2 to B8)

The Following components are initially introduced into a vessel:

86.0 g  of water 8.0 g of dispersant Lopon ® 890; BK Guilini Chemie GmbH& Co. OHG 2.0 g of dispersant 2-amino-2-methylpropanol (90% in water)2.0 g of antifoam Agitan ® 295; Münzing-Chemie GmbH, Heilbronn 2.0 g ofpreservative Mergal ® K 10 N; Troy Chemie GmbH, Seelze 3.0 g ofconcentrated ammonia solution (25%)

The following are added to these with stirring:

210.0 g of titanium dioxide pigment Kronos ® 2300; Kronos Titan GmbH,Leverkusen

The components are mixed for 20 minutes in a high-speed disperser. Thefollowing components are then added with stirring:

528.3 g of polymer dispersion A from I.) or V2 (53.0% strength byweight) 113.7 g of water  25.0 g of a 30% strength by weight aqueoussolution of an acrylate thickener; Mowlith ® VDM 7000; Clariant  20.0 gof wax dispersion (30% in water) Südranol ® 240; SüddeutscheEmulsions-Chemie GmbH Chemische Fabrik, Mannheim

The PVC of the solvent- and plasticizer-free dispersion finish is 16.8%.The results of testing of the performance characteristics are summarizedin table 4.

The dispersion finishes according to the invention of examples B2 to B8clearly show that, in comparison with a heterogeneous vinylacetate/ethene copolymer dispersion known from the prior art indispersion finishing sample B1 and a commercial homogeneous vinylacetate/ethene copolymer dispersion in example 9, solvent- andplasticizer-free dispersion finishes which are distinguished by asubstantially improved performance profile, in particular increasedblocking resistances and in some cases improved gloss properties, can beprepared owing to the heterogeneity according to the invention andpredominant stabilization of the dispersions A2 to A8 according to theinvention with ionic components.

TABLE 4 Testing of performance characteristics of formulation IStabilization of the dispersion Σ M₅ ^(a)) Σ M₃ ^(c)) Gloss and and 20°Dispersion S₂ ^(b)) S₁ ^(d)) Blocking [scale finish Dispersion [%]^(e))[%]^(e)) resistance divs.] B1 (V¹⁾) A1 (V1^(g))) 3 0.7 5 53 B2 A2 0 2.62 52 B3 A3 0 2.6 2 56 B4 A4 0 2.6 1 50 B5 A5 0 2.6 3 54 B6 A6 0 2.6 2 54B7 A7 0 2.6 2 56 B8 A8 0 2.6 1 47 B9 (V¹⁾) V2^(g)) —^(h)) —^(h)) 5 49^(a))M₅: nonionic monomers; ^(b))S₂: nonionic emulsifiers; ^(c))M₃:Ionic monomers; ^(d))S₁: Ionic emulsifiers; ^(e))Stated percentages arebased on the total amount of the monomers used for the production of thedispersion; ^(f))Comparative example; ^(g))Comparative dispersion;^(h))not specified.

II.2 Solvent- and Plasticizer-free Emulsion Paint Having a PVC of 32.6%;Formulation (II) (Comparative Examples C1 and C9, Examples C2 to C8)

The following components were initially introduced into a vessel:

178.2 g  of water 2.0 g of rheology assistant hydroxyethylcellulosehaving a viscosity of 6 Pa · s (determined as a 1.9% strength solutionin water at 25° C.); Tylose ® H 6000 YP2; Clariant 4.1 g of dispersantLopon ® 894; BK Guilini Chemie GmbH & Co. OHG 4.1 g of antifoam Agitan ®295; Münzing-Chemie GmbH, Heilbronn 2.0 g of sodium hydroxide solution(10%) 2.0 g of preservative Mergal ® K 9 N; Troy Chemie GmbH, Seelze

The following are added to these with stirring:

202.5 g of titanium dioxide pigment Kronos ® 2190; Kronos Titan GmbH,Leverkusen 151.9 g of calcium carbonate, calcite precipitated, 1 μmcalcite, mean particle size 1 μm; Omya Carb extra-Cl; Omya GmbH, Cologne

The components are mixed for 20 minutes in a high-speed disperser. Thefollowing components are then added with stirring:

453.2 g of polymer dispersion A from I.) or V2 (53.0% strength byweight)

The PVC of the solvent- and plasticizer-free emulsion paint is 32.6%.The results of the testing of the performance characteristics aresummarized in table 5.

The emulsion paints according to the invention of examples C2 to C8clearly show that, in comparison with a heterogeneous vinylacetate/ethene copolymer dispersion known from the prior art in exampleC1, solvent-free and plasticizer-free emulsion paint having high bindercontents (PVC=32.6%), which are distinguished by a substantiallyimproved performance profile, can be prepared owing to the heterogeneityaccording to the invention and the predominant stabilization of thedispersions A2 to A8 according to the invention with ionic components.The improved blocking resistances compared with examples C1 and C9 andimproved gloss properties of examples C2 to C8 compared with C1, withcomparable abrasion properties, are to be singled out in particular.

TABLE 5 Testing of the performance characteristics of formulation IIStabilization of the dispersion Σ M₅ ^(a)) Σ M₃ ^(c)) Gloss and and 60°Emulsion S₂ ^(b)) S₁ ^(d)) Blocking Abrasion [scale paint Dispersion[%]^(e)) [%]^(e)) resistance resistance divs.] C1 (V¹⁾) A1 (V1^(g))) 30.7 5 1 25 C2 A2 0 2.6 3 1 29 C3 A3 0 2.6 2 1 30 C4 A4 0 2.6 1 2 26 C5A5 0 2.6 3 1 30 C6 A6 0 2.6 2 1 25 C7 A7 0 2.6 2 1 25 C8 A8 0 2.6 1 2 26C9 (V¹⁾) v2^(g)) —^(h)) —^(h)) 5 2 31 ^(a))M₅: nonionic monomers;^(b))S₂: nonionic emulsifiers; ^(c))M₃: Ionic monomers; ^(d))S₁: Ionicemulsifiers; ^(e))Stated percentages are based on the total amount ofthe monomers used for the production of the dispersion; ^(f))Comparativeexample; ^(g))Comparative dispersion; ^(h))not specified.

II.3 Solvent- and Plasticizer-free Emulsion Paint Having a PVC of 35.3%;Formulation (III) (Comparative Examples D1 and D9, Examples D2 to D8)

The following components are initially introduced into a vessel:

186.0 g  of water 2.1 g of rheology assistant hydroxyethylcellulosehaving a viscosity of 6 Pa · s (determined as 1.9% strength solution inwater at 25° C.); Tylose ® H 6000 YP2; Clariant 4.2 g of dispersantLopon ® 894; BK Guilini Chemie GmbH & Co. OHG 4.2 g of antifoam Agitan ®295; Münzing-Chemie GmbH, Heilbronn 2.1 g of sodium hydroxide solution(10%) 2.1 g of preservative Mergal ® K 9 N; Troy Chemie GmbH, Seelze

The following were added to these with stirring:

211.4 g of titanium dioxide pigment Kronos ® 2190; Kronos Titan GmbH,Leverkusen 158.6 g of calcium carbonate, calcite 1 μm, calcite having amean particle size of 1 μm; Omya Carb extra-CL; Omya GmbH, Cologne

The components are mixed for 20 minutes in a high-speed disperser. Thefollowing components are then added with stirring:

 15.9 g of rheology assistant: 20% strength by weight aqueous solutionof an associatively thickening polyurethane; Tafigel ® PUR 50;Münzing-Chemie GmbH, Heilbronn 420.0 g of polymer dispersion A from I.)or V2 (53.0% strength by weight)

The PVC of the solvent- and plasticizer-free emulsion paint is 35.3%.The results of the testing of the performance characteristics aresummarized in table 6.

The emulsion paints according to the invention of examples D2 to D8clearly show that, in comparison with a heterogeneous vinylacetate/ethene copolymer dispersion known from the prior art in exampleD1 and a commercial homogeneous vinyl acetate/ethene copolymerdispersion in example D9, solvent- and plasticizer-free emulsion paintshaving a high binder content (PVC=35.5%), which is distinguished by asubstantially improved performance profile, can be prepared owing to theheterogeneity according to the invention and predominant stabilizationof the dispersions A2 to A8 according to the invention with ioniccomponents. The improved blocking resistances compared with examples D1and D9 and the improved gloss properties of examples D2 to D8 comparedwith D1, with comparable abrasion properties, are to be singled out inparticular.

TABLE 6 Testing of the performance characteristics of formulation IIIStabilization of the dispersion Σ M₅ ^(a)) Σ M₃ ^(c)) Gloss and and 60°Emulsion S₂ ^(b)) S₁ ^(d)) Blocking Abrasion [scale paint Dispersion[%]^(e)) [%]^(e)) resistance resistance divs.] D1 (V¹⁾) A1 (V1^(g))) 30.7 5 1 18 D2 A2 0 2.6 2 1 23 D3 A3 0 2.6 3 1 23 D4 A4 0 2.6 1 2 20 D5A5 0 2.6 3 1 26 D6 A6 0 2.6 1 1 20 D7 A7 0 2.6 2 1 23 D8 A8 0 2.6 1 2 19D9 (V¹⁾) 2^(g)) —^(h)) —^(h)) 5 1 26 ^(a))M₅: nonionic monomers;^(b))S₂: nonionic emulsifiers; ^(c))M₃: Ionic monomers; ^(d))S₁: Ionicemulsifiers; ^(e))Stated percentages are based on the total amount ofthe monomers used for the production of the dispersion; ^(f))Comparativeexample; ^(g))Comparative dispersion; ^(h))not specified.

II.4 Solvent- and Plasticizer-free Emulsion Paint Having a PVC of 75.6%;Formulation (IV) (Comparative Examples E1 and E9, Examples E2 to E5)

The following components are initially introduced into a vessel:

248.0 g  of water 3.0 g of rheology assistant methylhydroxyethyl-cellulose having a viscosity of 30 Pa · s (determined as a 1.9% strengthsolution in water at 25° C.); Tylose ® MH 30000 YP2; Clariant GmbH,Frankfurt 13.0 g of a 10% strength by weight solution of a sodiumpolyphosphate in water, Calgon ®; BK Guilini Chemie GmbH & Co. OHG 3.0 gof dispersant Lopon ® 894; BK Guilini Chemie GmbH & Co. OHG 4.0 g ofantifoam Agitan ® VP 315; Münzing-Chemie GmbH, Heilbronn 2.0 g of sodiumhydroxide solution (10%) 4.0 g of preservative Mergal ® K 9 N; TroyChemie GmbH, Seelze 5.0 g of rheology additive: 10% strength by weightaqueous solution of a hectorite; Hectone H; G.M. Langer & Co. GmbH,Ritterhude

The following are added to these with stirring:

100.0 g of mica, 50 μm mica MU-N 85; Ziegler & Co. GmbH, Wunsiedel 100.0g of calcium carbonate, precipitated, 0.3 μm Socal P2; Deutsche SolvayGmbH, Solingen  25.0 g of aluminum silicate, 2.5 μm kaolin china gradeB; Imerys, St. Austell, Cornwall, England  90.0 g of calcium carbonate,calcite 2 μm, calcite having a mean particle size of 2 μm; Omya Carb 2GU; Omya GmbH, Cologne  90.0 g of calcium carbonate, calcite 5 μm,calcite having a mean particle size of 5 μm; Omya Carb 5 GU; Omya GmbH,Cologne 185.0 g of titanium dioxide pigment Kronos ® 2160; Kronos TitanGmbH, Leverkusen

The components are mixed for 20 minutes in a high-speed disperser. Thefollowing components are then added with stirring:

130.0 g of polymer dispersion A from I.) or V2 (53.0% strength byweight)

The PVC of the solvent- and plasticizer-free interior paint is 75.6%.The results of the testing of the performance characteristics aresummarized in table 7.

Examples E2 to E5 according to the invention make it clear that,compared with a heterogeneous vinyl acetate/ethene copolymer dispersionA1 known from the prior art and a commercial, homogeneous vinylacetate/ethene copolymer dispersion V2, the dispersions A2 to A5according to the invention exhibit substantially improved performancecharacteristics in solvent- and plasticizer-free binder-rich coatingsystems (cf. tables 3 to 6) and moreover permit the preparation ofsolvent- and plasticizer-free interior paints (PVC=75.6%) which arecomparable in their performance profiles to heterogeneous vinylacetate/ethene copolymer dispersions known from the prior art (cf.example E1).

TABLE 7 Testing of the performance characteristics of the formulation IVStabilization of the dispersion Σ M₅ ^(a)) Σ M₃ ^(c)) and and EmulsionS₂ ^(b)) S₁ ^(d)) Blocking Abrasion paint Dispersion [%]^(e)) [%]^(e))resistance resistance E1 (V¹⁾) A1 (V1^(g))) 3 0.7 0 11 E2 A2 0 2.6 0 10E3 A3 0 2.6 0 10 E4 A4 0 2.6 0 11 E5 A5 0 2.6 0 11 E6 A6 0 2.6 0 7 E7 A70 2.6 0 8 E8 A8 0 2.6 0 8 E9 (V¹⁾) v2^(g)) —^(h)) —^(h)) 0 8 ^(a))M₅:nonionic monomers; ^(b))S₂: nonionic emulsifiers; ^(c))M₃: Ionicmonomers; ^(d))S₁: Ionic emulsifiers; ^(e))Stated percentages are basedon the total amount of the monomers used for the production of thedispersion; ^(f))Comparative example; ^(g))Comparative dispersion;^(h))not specified.

In addition, examples E6 to E8 according to the invention show that,over and above their advantageous properties in solvent- andplasticizer-free binder-rich coating systems (cf. tables 3 to 6), theheterogeneous dispersions A6 to A8 according to the invention which arepredominantly stabilized by ionic components and contain silanes in theform of copolymerized units can be used for the preparation of solvent-and plasticizer-free interior paints which have improved abrasionresistances compared with an interior paint which was formulated using aheterogeneous vinyl ester/ethene dispersion corresponding to the priorart (E1). Said abrasion resistances correspond to the abrasionresistances as can be achieved with a commercial homogeneous vinylester/ethene dispersion (E9).

III. Determination of the Performance Characteristics

III.1.1 Surface Tack of Dried Dispersion Films

For testing the surface tack of dried dispersion films produced from thedispersion A, glass plates (5 cm×20 cm) are coated with thecorresponding dispersions with the aid of a box-type doctor blade (wetlayer thickness: 200 μm). After drying for 24 hours under standardconditions (23° C., 50% relative humidity), the surface tack is carriedout with the aid of a Polyken Probe Tacktester (TMI). For this purpose,the ram of the tack tester is pressed with a contact pressure of 5.1×10⁴N/m² for 20 seconds onto the dispersion film to be investigated and,after this time, pulled perpendicularly away from the surface at a speedof 1 cm/sec. The force which is required to separate the ram from thesurface of the dispersion film is determined.

Evaluation:

Rating 1: 0 N/m²; rating 2: 0.01×10⁴ to 2.5×10⁴ N/m²; rating 3: 2.51×10⁴to 5.1×10⁴ N/m²; rating 4: 5.11×10⁴ to 7.6×10⁴ N/m²; rating 5: 7.61×10⁴to 10.20×10⁴ N/m²; rating 6: >10.20×10⁴ N/m².

The surface tack thus increases with increasing rating.

III.2. Blocking Resistance of Dried, Pigment-containing Coatings

For testing the blocking resistance of the formulations I, hiding powercards from BYK Malinckrodt or Morest are coated with the correspondingemulsion paints (wet layer thickness: 200 μm). After drying for 24 hoursat 50° C., two coated cards are placed with their coated side one on topof the other and loaded with 0.78×10⁴ N/m² for 0.5 hour at roomtemperature. The force required for separating the coated cards from oneanother again is then determined.

For testing the blocking resistance of the formulations II, III and IV,hiding power cards from BYK Malinckrodt or Morest are coated with thecorresponding emulsion paint (wet layer thickness: 200 μm). After dryingfor 24 hours under standard conditions (23° C., 50% relative humidity),two coated cards are placed with their coated side one on top of theother and loaded with 3.1×10⁴ N/m² for 0.5 hour at room temperature. Theforce required for separating the coated cards from one another again isthen determined.

Evaluation of the blocking resistance of the formulations I to III:

Rating 0: 0 N/m²; rating 1: 0.1×10⁴ to 0.8×10⁴ N/m²; rating 2: 0.81×10⁴to 1.6×10⁴ N/m²; rating 3: 1.61×10⁴ to 2.4×10⁴ N/m²; rating 4: 2.41×10⁴to 3.20×10⁴ N/m²; rating 5: >3.20×10⁴ N/m².

The blocking resistance thus decreases with increasing rating.

III.3. Gloss of Dried, Pigmented Coatings

For testing the gloss, hiding power cards from BYK Malinckrodt or Morestare coated with the corresponding emulsion paint (wet layer thickness:200 μm). After. drying for 24 hours under standard conditions (23° C.,50% relative humidity), the gloss of these coatings is determined usinga laboratory reflectometer RL (reflectometer measuring head RL) from Dr.Bruno Lange GmbH at angles of 20°, 60° and 85°.

The gloss properties increase with increasing reflectometer values.

III.4. Abrasion Resistance of Dried, Pigmented Coatings

The abrasion resistances for the paint formulations II, III and IV aredetermined according to European Standard 13300 by means of a model 494abrasion tester from Erichsen with adapter set for abrasion testsaccording to ISO 11998. Abrasion pads (3M Scotch Brite Handpad 7448,type S ultra fine) having dimensions of 39×90 mm serve as a standardizedabrasion medium. The emulsion paints are applied to Leneta films using afilm drawing apparatus model 509/1 from Erichsen with a doctor bladehaving a gap height of 200 μm. The films are then dried under standardconditions (23° C., 50% relative humidity) in a conditioned chamber for28 days. The dry layer thickness is about 130 μm (formulation II), 120μm (formulation III) or 160 μm (formulation IV). Test specimens having alength of 430 mm and a width of at least 80 mm are cut from the coatedLeneta film and weighed. After the test specimens have been clamped inthe abrasion machine, the wash liquid (0.25% strength by weight solutionof sodium dodecylbenzenesulfonate in distilled water) is applied to thesurface of the paint film with the aid of a soft brush. Thereafter, theabrasive pad is impregnated with the wash liquid until the pad weight,including wash liquid, is from 3.5 to 4.5 g. After the wash liquidapplied by means of the brush has acted for 60 seconds, the paint filmis subjected to an abrasive load with the unprinted side of theimpregnated abrasive pad for 200 abrasion cycles.

Immediately after the end of the 200 abrasion cycles, the test specimenis cleaned with a gentle water jet to remove abraded particles and isdried under standard conditions until the weight is constant. The weightloss is determined on an analytical balance and is shown as a weightloss per unit area, which can be determined on the basis of the abradedarea of 148 cm², which is obtained from the pad width of 3.9 cmmultiplied by the length of 38 cm covered. Evaluation of the weight lossper unit area:

Rating 0: 0 mg/cm²; rating 1: 0.01 to 1.0 mg/cm²; rating 2: 1.01 to 2.0mg/cm²; rating 3: 2.01 to 3.0 mg/cm²; rating 4: 3.01 to 4.0 mg/cm²;rating 5: 4.01 to 5.0 mg/cm²; rating 6: 5.01 to 6.0 mg/cm²; rating 7:6.01 to 7.0 mg/cm²; rating 8: 7.01 to 8.0 mg/cm²; rating 9: 8.01 to 9.0mg/cm²; rating 10: 9.01 to 10.0 mg/cm²; rating 11: 10.01 to 11.0 mg/cm²;rating 12: 11.01 to 12.0 mg/cm²; rating 13: >12.0 mg/cm².

The abrasion resistance of the coatings thus decreases with increasingrating.

1. An aqueous plastic material dispersion based on a vinyl estercopolymer P obtained by multistage emulsion polymerization with a solidcontent of up to 80% by weight and a minimum film formation temperaturebelow 20° C., which is substantially stabilized by ionic components, thevinyl ester copolymer P comprising at least one homo- or copolymer A andat least one homo- or copolymer B, and the homo- or copolymer A having aglass transition temperature of 0 to 20° C. and the homo- or copolymer Bhaving a glass transition temperature of 20 to 50° C., provided that theglass transition temperatures of the two homo- or copolymers A and Bdiffer by at least 10 K, the sum of the amounts of the homo- orcopolymers A and B in the vinyl ester copolymer P being at least 50% byweight, based on the copolymer P, the weight ratio of homo- or copolymerA to homo- or copolymer B being 95/5 to 5/95 and the homo- or copolymersA and B, independently of one another, containing in the form ofcopolymerized units a) from 50 to 100% by weight of at least one vinylester of carboxylic acids of 1 to 18 carbon atoms (M1) and b) from 0 to25% by weight of at least one monoethylenically unsaturated, optionallyhalogen-substituted hydrocarbon of 2 to 4 carbon atoms (M2), based onthe total mass of the monomers used for the preparation of therespective homo- or copolymer A and B, wherein it comprises, based onthe total mass of the monomers used for the preparation of the vinylester copolymer P, from 0 to 10% by weight of at least one ethylenicallyunsaturated, ionic monomer (M3) and from 0 to 5% by weight of ionicemulsifiers (S1), the total mass of ethylenically unsaturated, ionicmonomers (M3) and ionic emulsifiers (S1) being at least 2%.by weight. 2.The plastic material dispersion of claim 1, wherein it has a solidscontent of from of 20 to 80% by weight.
 3. The plastic materialdispersion of claim 1 wherein the sum of the amounts of the homo- orcopolymers A and B in the vinyl ester copolymer P is from 75 to 100% byweight, based on the total mass of the copolymer P.
 4. The plasticdispersion of claim 1 wherein it has a pH in the range of 2 to
 9. 5. Theplastic material dispersion of claim 1 wherein the homo- or copolymers Aand/or B contain, as vinyl esters of carboxylic acids of 1 to 18 carbonatoms (M1) incorporated in a form selected from the group consisting ofpolymerized units, vinyl esters of carboxylic acids of 1 to 8 carbonatoms, vinyl esters of saturated, branched, monocarboxylic acids of 9,10 or 11 carbon atoms in the acid, vinyl esters of relativelylong-chain, saturated and unsaturated fatty acids, vinyl esters ofbenzoic acid and of p-tert-butylbenzoic acid and mixtures thereof. 6.The plastic material dispersion of claim 1 wherein the homo- orcopolymers A and/or B contain vinyl acetate as vinyl esters ofcarboxylic acids of 1 to 18 carbon atoms (M1) incorporated in the formof polymerized units.
 7. The plastic material dispersion of claim 1wherein the copolymers A and/or B contain ethene as monoethylenicallyunsaturated hydrocarbons of 2 to 4 carbon atoms (M2) incorporated in theform of copolymerized units.
 8. The plastic material dispersion of claim1 wherein the amount of monoethylenically unsaturated hydrocarbons of 2to 4 carbon atoms (M2) in the vinyl ester copolymer P is less than 20%by weight, based on the total mass of the monomers used for thepreparation of the vinyl ester copolymer P.
 9. The plastic materialdispersion of claim 1 wherein the homo- or copolymers A and/or Bcontain, as ethylenically unsaturated, ionic monomers (M3) incorporatedin the form of copolymerized units, unsaturated monocarboxylic acids,unsaturated dicarboxylic acids or the monoesters thereof with alkanolsof 1 to 12 carbon atoms, unsaturated sulfonic acids and/or unsaturatedphosphonic acids.
 10. The plastic material dispersion of claim 1 whereinthe vinyl ester copolymer P contains, incorporated as copolymerizedunits, up to 5% by weight, based on the total mass of the monomers usedfor the preparation of the vinyl ester copolymer P, at least oneunsaturated, copolymerizable organic silicon compound (M4).
 11. Theplastic material dispersion of claim 10 wherein monomers containingsiloxane groups and of the formula RSi(CH₃)₀₋₂(OR¹)₃₋₁, in which R hasthe meaning CH₂═CR²—(CH₂)₀₋₁ or CH₂═CR²CO₂—(CH₂)₁₋₃, R¹ is anunsubstituted or substituted alkyl of 3 to 12 carbon atoms, which may beinterrupted by an ether group, and R² is —H or —CH₃, are used asunsaturated, copolymerizable organosilicon compounds (M4).
 12. Theplastic material dispersion of claim 1 wherein the vinyl ester copolymerP contains, incorporated in the form of copolymerzied units, up to 5% byweight of ethylenically unsaturated, nonionic monomers (M5), based onthe total mass of the monomers used for the preparation of the vinylester copolymer P.
 13. The plastic material dispersion of claim 1wherein the vinyl ester copolymers P contain, incorporated in the formof copolymerized units, up to 30% by weight of at least one further,ethylenically unsaturated monomer (M6), based on the total mass of themonomers used for the preparation of the vinyl ester copolymer P. 14.The plastic material dispersion of claim 1 wherein it contains from 0.1to 4% by weight of ionic emulsifiers (S1), based on the total mass ofthe monomers used for the preparation of the vinyl ester copolymer P.15. The plastic material dispersion as of claim 1 wherein it containsanionic emulsifiers as ionic emulsifiers (S1).
 16. The plastic materialdispersion of claim 15, wherein it contains alkali metal and ammoniumsalts of alkylsulfates, alkylphosphonates, sulfuric monoesters orphosphoric mono- and diesters of ethoxylated alkanols and ethoxylatedalkyiphenols, of alkanesulfonic acids and alkylarylsulfonic acids,and/or compounds of the formula

in which R¹ and R² are hydrogen or alkyl of 4 to 24 carbon atoms and arenot both simultaneously hydrogen and X and Y are independently alkalimetal ions or ammonium ions, as anionic emulsifiers.
 17. The plasticmaterial dispersion of claim 1 wherein it contains nonionic emulsifiers(S2).
 18. The plastic material dispersion of claim 12 wherein the ratioof the total amount of ionic components (M3) and (S1) to the totalamount of nonionic components (M5) and (S2) used does not fall below thevalue 1 .
 19. A method for producing a plastic material dispersionpreparing first the homo- or copolymer B by aqueous free radicalemulsion polymerization and then preparing the homo- or copolymer A inthe aqueous dispersion of the homo- or copolymer B.
 20. An aqueousformulation for coating substrates, comprising a plastic materialdispersion of claim
 1. 21. A pigment-containing, aqueous formulationcomprising a plastic material dispersion of claim
 1. 22. An emulsionpaint, comprising a plastic material dispersion of claim
 1. 23. A foodcoating, comprising a plastic material dispersion of claim
 1. 24. Apaper coating slip, comprising a plastic material dispersion of claim 1.25. In a process for coating substrates with an aqueous formulation, theimprovement comprising adding the plastic material dispersion of claim 1to the aqueous formulation.
 26. In a process for coating substrates withpigment-containing aqueous formulations, the improvement comprisingadding the plastic material dispersion of claim 1 to the formulations asa binder.
 27. In a process for coating substrates with an emulsionpaint, the improvement comprising adding the plastic material dispersionof claim 1 to the emulsion paint as a binder.
 28. In a process forpreparing at least one member of the group consisting of syntheticresin-bound renders, tile adhesives, coating materials, joint sealingcompounds, sealing compounds and paper coating slips, the improvementcomprising adding the plastic material dispersion of claim 1 as abinder.